JPH0465409A - Surface-modifying agent for polymeric material curable with actinic energy ray and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject modifier having excellent surface orientation and exhibiting excellent properties such as water and oil repellency caused by using fluorine-containing polymer over an extremely long period by reacting (meth)actylic acid to a fluorine-containing block copolymer produced by a specific method. CONSTITUTION:A monomer of formula I [R3 is H, CH2COOH, etc.; R4 is COOR5 (R5 is H, group of formula II, etc.), CN, etc.] and a monomer of formula III (R8 is H or methyl) are copolymerized at a weight ratio (I/III) of 99/1 to 40/60 using a polymeric peroxide as a polymerization initiator. A monomer of formula IV [R1 is H or methyl R2 is CpH2p (p is 1-10), CH2CH2O, etc.; Rf is CnF2n+1, (CF2)nH (n is 1-16), etc.] is polymerized in the presence of the copolymer produced by the 1st step. The weight ratio of the monomers used in the 1st state polymerization to the 2nd stage polymerization is selected to be 90/10 to 20/80. Finally, a compound of formula V [R9 is CH2=CH or CH2=CH3] is reacted to the glycidyl group of the resultant fluorine-containing polymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is particularly applicable to paints, inks, adhesives, pressure-sensitive adhesives, sealants, and plate-making materials that harden when irradiated with active energy rays such as ultraviolet rays and electron beams. This article relates to surface modifiers for polymeric materials such as, and methods for producing the same, and in detail, it shows excellent surface orientation and chemically bonds to the polymeric material to be surface modified through unsaturated groups. The present invention relates to an active energy ray-curable surface modifier for polymeric materials that can exhibit properties derived from the fluoropolymer portion for an extremely long period of time, and a method for producing the same.

[Conventional technology]

The present inventors have previously proposed that by applying a fluorine-containing block copolymer as a surface modifier for a polymer material, the function of the fluorine-containing polymer moiety can be imparted to the surface of the polymer material. For example, in Japanese Patent Application Laid-open No. 60-22410,
When a fluorine-containing block copolymer is added to a polymer material,
The fluorine-containing block copolymer is oriented on the surface and can impart excellent properties such as water and oil repellency and stain resistance possessed by perfluoroalkyl groups to the material surface, and the modification effect is excellent in sustainability. It is shown. It is also known to be useful as an anti-blocking agent (Japanese Unexamined Patent Publication No. 2-4877) and as a moisture-proofing agent (Japanese Unexamined Patent Publication No. 2-4812).

The properties of perfluoroalkyl groups are often required not only for thermoplastic resins and thermosetting resins but also for active energy ray-curable resins.

For example, UV curable paints are required to have antifouling properties, water and oil repellency, solvent resistance, etc., and UV curable adhesives and adhesives are sometimes required to have water resistance, acid resistance, moisture resistance, etc. Furthermore, UV curable inks used for printing plastic bottles and the like are required to have water resistance, and solder resist materials and the like are required to have moisture resistance. The present inventors have proposed that fluorine-containing block copolymers are also useful as modifiers for such materials (Japanese Unexamined Patent Publication No. 2-4812).

There are a large number of proposals regarding materials that are sensitive to active energy rays, but among them, there are some that are intended to be used as resist materials and coating materials.
Proposals regarding active energy ray-sensitive fluoropolymers have also been made. For example, JP-A-58-215411 proposes that a fluorine-containing sensitive material can be obtained by a radical copolymerization reaction between a monomer having photodimerization reactivity in its side chain and a fluorine-containing monomer. ing.

Also, JP-A-62-25104, JP-A No. 63-30126
No. 8 discloses a fluoropolymer obtained by copolymerizing a hydroxyl group-containing vinyl ether and a fluoroolefin;
It has been reported that a polymer that can be cured by active energy rays can be obtained by reaction with a compound having an isocyanate group and an unsaturated group. Furthermore, JP-A-62-19026
No. 4 discloses a coating composition containing a polymer obtained from a reaction between three components: a fluorine-containing block copolymer having an OH group, an isocyanate compound, and a compound having an OH group and an unsaturated group. Disclosed.

[Problem to be solved by the invention]

As mentioned above, the surface of active energy ray-curable resins can be modified by using fluorine-containing block copolymers with excellent surface orientation. In this case, the effect of polymer entanglement between the fluorine-free polymer part, which is one polymer chain of the fluorine-containing block copolymer, and the resin to be modified provides good sustainability of the modification effect. However, if the two could be covalently bonded, the durability would be further improved.

To achieve this purpose, Japanese Patent Application Laid-Open No. 6219026
Publication No. 4 has already proposed a fluorine-containing block copolymer containing unsaturated groups, but this proposal adopts a method of introducing unsaturated groups through a reaction using an isocyanate compound. Therefore, there is a problem that gelation tends to occur during the reaction. Although gelation of fluorine-containing block copolymers and unsaturated group-containing compounds tends to be suppressed by using a large amount of inocyanate compounds, when synthesized using such a large amount of isocyanate compounds, There is a problem that as the fluorine block copolymer increases in quantity, the molecular weight increases, and the ratio of the fluorine-containing polymer portion decreases, resulting in a decrease in surface performance.

Even if the fluorine-containing block copolymer is functional when used for a specific application as in this proposal, it is difficult to use it as a surface modifier for a wide range of active energy ray-curable resins. There were some problems, and further improvements were desired.

The present invention was made to solve the above problems, and its purpose is to have both excellent surface orientation and sensitivity to active energy rays, and to make the surface of an active energy ray-curable polymer material repellent and water-repellent. The object of the present invention is to provide an active energy ray-curable surface modifier for polymeric materials that can permanently impart functions such as oiliness, antiblocking properties, and moisture resistance, and a method for producing the same.

[Failure to solve the problem]

In the first aspect of the present invention, a structural unit (A) derived from the following general formula (I), a polymer portion derived from the following general formula (II), and the following general formula (III) are used as a unit. It consists of a structural unit (B) consisting of a polymer part having the general formula (III), and the proportion of the polymer part having the general formula (III) in the structural unit (B) is 1 to 70% by weight, and the structural unit (A
)/structural unit (B) ratio is 80/20 to 10 by weight
/90 block copolymer is employed.

CH22CRICOOR2Rf... (I) In the formula, R1 is a hydrogen atom or a methyl group, R2 is CP H4F
, C(CPH2P+□)H--CH2C(Cp
Hzp++) H- or -CH2CH20-Rf is C-
F2a+1. (CF2)-H, (CF2)pOc,
R2,,c+F2+++, (CF2)POC,Ht
mc+F2+H.

R7 (wherein R6 is a hydrogen atom or CPH2P+l! R
7 is a hydrogen atom, linear or branched CPH2P+1, or CH20H. However, p is an integer from 1 to IO. ), -CON 0l-CONHC (C(-1)).

is 0 to I H2, where p is 1 to 10. n is 1-162m091 is 0-1
It is an integer of 6.

CR3R4... (If) R3 is a hydrogen atom, a methyl group, or CH20COCfiH
2-+1 (In the formula, n is an integer of 1 to 16, and may be either linear or branched.) (CHCRs)-...
......(III) Straight chain or branched Ct H
2n+1+ linear or branched CrH2p++OH,
CH2CH(OH)CH3, (C2H40)ycsH2
s++.

CCH2CH(CH3)○]rcsHzs+1.

However, P is 1 to 10. n is 1 to 16. r is 2-20, s
is an integer from 0 to 8. ), -CONR,,.

In the formula, R8 is a hydrogen atom or a methyl group, and R9 is CH2=
CH, CH2=C(CH3)-.

Further, in the second invention, in the first invention, the structural unit (,A) is a polymer part derived from general formula (I) in an amount of 40% or more and a polymer part derived from general formula (II). A method is adopted in which the content is 60% by weight or less.

Furthermore, in the third invention, in the first stage polymerization in the first or second invention, a polymeric peroxide is used as a polymerization initiator, and one or more monomers represented by the general formula (II) are used as a polymerization initiator. and the monomer represented by the following general formula ((IV)), the weight ratio of which is the monomer represented by the general formula (II)/-monomer represented by the general formula TV)- 99/1-4
After polymerization under 0/60 conditions, in the second stage polymerization,
The weight ratio of one or more monomers represented by the general formula (I) used in the first stage polymerization and the second stage polymerization is 90/'10 to 20/'. 80 and the following general formula (
The block copolymer is produced by reacting the glycidyl group in the fluorine-containing polymer with the compound represented by formula (V).

In the formula, R8 is a hydrogen atom or a methyl group.

R9-COOH...(V) In the formula, R0 is CH2=CH-, CH2=C(CH3)-
It is.

Further, in a fourth invention, in the third invention, in the second stage polymerization, 40% by weight or more of one or more monomers represented by the general formula (I) and the general formula ( A method of copolymerizing one or more monomers represented by II) with 60% by weight or less is adopted.

Next, each component of the present invention will be explained.

First, the structural unit (A) in the block copolymer of the present invention
I will explain about it. In order for the block copolymer to have sufficient surface activity and function as a fluoropolymer, this structural unit is a polymer derived from the general formula (T) in the first and third inventions. In the second and fourth inventions, the polymer portion 40 derived from the general formula (1) is
% by weight or more, and 60% by weight or less of a polymer portion derived from the general formula (II). Structural unit (A)
If the polymer portion is composed of less than 40% by weight of the polymer derived from the general formula (1), the surface active ability decreases and the function as a surface modifier is insufficient.

In the general formula (I), if p and m exceed 10, the properties derived from the perfluoroalkyl group will decrease, which is not preferable. Furthermore, when n and l exceed 16, it is not preferable because production is not easy and the properties derived from the perfluoroalkyl group are not necessarily good. p is 1
-4, m is 0-4, n and l are 1-10, and it is more preferable that the terminal of the perfluoroalkyl group is -CF a.

As the monomer represented by the general formula (I), the following monomers can be suitably used, particularly from the viewpoint of ease of production.

CFs (CF2) 7CH2CH20C0-CH
=CH2 CF3CH20COCH=CH2, CFa (CF2)4CH2CH20COC(CH3)
= CH2 C7F15CON (C2H6)CH20COC(C
Hs ) = CH2 CF3 (CF2)tsOtN (CH3)CHzC
HtOCOCH= CH2 CZF 6802N (C3H7)CHtCHzOC
OC(CHs) = CH2 CeF +aS 02N (C2H5)C2H40C
OC(CH3) = CH2 In addition to the above monomers, the following monomers can also be used.

(CF3) ICF (CF2) a (CH2) a
-OCOCR=CH2 (CFa)2CF (CF2)to (CH2)a-O
COC(CH3)=CH2 CF a (CF z) 4CH(CH3)OCOC(
CHa) = CH2 CF sCH20CH2CH20COCH= CH2C
2F 5 (CH2CH20)2CH20COCH=
CH2 (CF3)2CF O(CHz)sOCOCH= CH
2 CFa (CF,)40CH2CH! 0COC(CH3
)=CHz CzF 6CON (CtHs)CHtOCOCH=
CH2 CF a (CF 2)2CON (CH3)CH(
CHs) CHz OCOCH= CH2H(CF2
)sC(C2H5)OCOC-(CH3)=CH2H(CFz)8CH20COCH=CH2H(CF2)
4CH20COCH=CH2H(C-F2)scHzo
coc- (CH3) = CH2 CF3 (CF2)7SO2N (CH3)CH2C
H20COC(CH3) -CH2CFs (CFz
)7SO2N (CHs) (CHz) 1oOCO
CH= CHtCzF sS OzN (C2H6)
CHtCHtOCOC(CHs)= CH= CH2(CF2)7SO2N (CH3)(CH2)
40COCH=CH2 C2F5SO2N (C2H5)C(C2H5)HC
H20COCH" CH2 One or more of these monomers may be selected as appropriate and used.

Next, the monomer represented by general formula (II) is used to constitute the structural unit (A) in the second and fourth inventions,
In the first to fourth inventions, it is an essential component constituting the structural unit (B). Specifically, the monomer represented by the general formula (■) includes methyl acrylate and/or methyl methacrylate [hereinafter collectively referred to as methyl (meth)acrylate. The same applies below] Ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
(meth)acrylic acid glycidyl, (meth)acrylic acid n
-butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-(meth)acrylate
Ethylhexyl, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, -N,N-dimethyl (meth)acrylate (meth)acrylic esters such as aminoethyl, (meth)acrylic acids such as hydroxylethyl (meth)acrylate, hydroquinepropyl (meth)acrylate, and -3-chloro-2-hydroxypropyl (meth)acrylate; Polyethylene glycol or polypropylene glycol esters of (meth)acrylic acid such as hydroquine ester, (meth)acrylic acid triethylene glycol ester, and (meth)acrylic acid dipropylene glycol ester can be suitably used.

In addition to these monomers, styrene, vinyltoluene, α-
Aromatic vinyl monomers such as methylstyrene, carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl stearate, (meth)acrylamide, N-methylol (meth)acrylamide, N,N
- Vinyl monomers containing amide groups such as dimethyl (meth)acrylamide, N-(meth)acryloylmorpholine, 2-acrylamide-2-methylpropanesulfonic acid,
(Meth)acrylic acid, itaconic acid, etc. can be used. One or more of these monomers may be appropriately selected and used.

Next, the structural unit (B
) will be explained.

It is essential that the structural unit (B) has the above general formula (I) as a constituent component in order to exhibit sensitivity to active energy rays. The proportion of the polymer portion having general formula (m) as a unit in the structural unit (B) is 1 to 70% by weight.
Within this range, it is determined as appropriate depending on the purpose of use of the block copolymer of the present invention, the type of unsaturated group, etc. In the case of any unsaturated group, the general formula (III
) is less than 1% by weight, sensitivity tends to be insufficient. In addition, it is not necessary to exceed 70% by weight in order to form a chemical bond with the polymeric material that is the target of surface modification, but if it exceeds 70% by weight, problems may occur in the pot life depending on the type of unsaturated group. . This ratio is 3
~45% by weight is preferred.

Further, the structural unit (B) is configured with the general formula (II) as an essential component so that appropriate miscibility can be achieved depending on the polymer material to be modified. The quality of this miscibility can be determined by visual inspection after mixing the polymeric material and the surface modifier of the present invention and forming a film. That is, if the film is transparent, or even if it is not transparent, there is no separation when mixed and a uniform film is obtained, it is judged to have appropriate miscibility.

Next, the structural unit (A
) and structural unit (B) weight ratio is 80/20 to 10/9
It is 0. If the proportion of the structural unit (A) exceeds 80% by weight, sensitivity to active energy rays may decrease or problems may arise in miscibility with the resin. On the other hand, when the ratio of the structural unit (A) is less than 10% by weight, the function of fluorine derived from the structural unit (A) cannot be fully expressed.

Next, methods for producing active energy ray-curable surface modifiers for polymeric materials according to the third and fourth aspects of the invention will be described.

The surface modifier of the present invention is particularly characterized by ease of industrial productivity,
From a wide range of performance aspects, a structural unit (B") having a humanoxol group in its side chain and a structural unit (, A) The fluorine-containing block copolymer having
Synthesized by suspension polymerization method, solution polymerization method, emulsion polymerization method, etc.
Then, by an addition reaction with a compound represented by the general formula (V), an unsaturated group is produced.

The above-mentioned polymeric peroxide may be any compound having two or more peroxy bonds in one molecule, and specifically, for example, Japanese Patent Publication No. 63-54 filed by the present inventors.
Those described in JP-A-239, JP-A-60-22410, etc. can be suitably used.

The performance as a surface modifier depends on the structure of the block copolymer, as mentioned in the explanation of the first and second inventions, but when producing a polymeric peroxide as a polymerization initiator, Since it depends on the manufacturing conditions, it is necessary to set appropriate conditions. However, if it is produced under appropriate conditions, it can sufficiently function as a surface modifier without removing by-product polymers other than the block copolymer.

The ratio of the monomer of general formula (II) and the monomer of general formula (IV) used in the first stage polymerization is 99/1 to 40/60, but if this ratio exceeds 99/1 , general formula (V)
The amount of unsaturated groups introduced based on the compound decreases, resulting in insufficient sensitivity to active energy rays. Also 40/
If it is less than 60, problems may occur in the pot life depending on the type of compound (V) and the reaction ratio between the fluorine-containing polymer and compound (V), and chemical bonding may occur with the polymer material that is the target of surface modification. There is also a problem in holding it. Therefore,
This range is 99/l to 40/60 and 97/3 to 5
Preferably it is 5/45.

Next, it is appropriate to start the second stage polymerization after the monomer charged during the first stage polymerization has almost completely disappeared.

For this purpose, a method is preferably employed in which the first stage polymerization is almost completed or the remaining monomer is removed by reprecipitation purification or the like. Further, during the first stage polymerization, it is necessary that a sufficient amount of peroxy bonds derived from the polymeric peroxide remain to carry out the second stage polymerization. In order for the surface modifier of the present invention to have sufficient surface activity and to effectively express the functions of the polymer portion formed in the second stage polymerization, the second stage polymerization is carried out by polymerizing the general formula (I). Or,
or 40% by weight or more of the general formula (I) and the general formula (
II) It is essential to copolymerize with 60% by weight or less. When the amount of the general formula (I) is less than 40% by weight, the surface activity of the surface modifier obtained decreases and the function as a surface modifier is insufficient.

Further, the ratio of monomers used in the first stage polymerization and the second stage polymerization is 90/10 to 20/80 by weight. In addition,
The monomers used in this case refer to those involved in polymer formation in the first and second stage polymerizations, and do not include unreacted monomers.

If this usage ratio exceeds 90/I 2 O, the surface orientation is insufficient and the function of fluorine cannot be fully expressed. On the other hand, if the ratio is less than 20/80, sensitivity to active energy rays may decrease or problems may arise in miscibility with the resin.

Furthermore, a fluorine-containing block copolymer into which an unsaturated group has been introduced can be obtained by an addition reaction between the fluorine-containing polymer and the compound represented by the general formula (V). As for the reaction conditions, the ratio of the amount of glycidyl groups contained in the structural unit (B') in the block copolymer to the compound (V) is 110°4 to 1/1.3 on a molar basis. Appropriate. If it is less than 110.4, there is a tendency that a good reaction rate cannot be achieved, which is not preferable. On the other hand, the higher the ratio of compound (V), the greater the amount of unsaturated groups introduced, but the process of removing excess compound (V) after the reaction becomes complicated.
Since it may remain as an impurity, it is appropriate that the ratio does not exceed 1/1.3.

Furthermore, in order to achieve sufficient reactivity and prevent the block copolymer from increasing in molecular weight due to polymerization of unsaturated groups, care must be taken to ensure that no peroxy bonds are present in the reaction system. Further, it is appropriate to use a known polymerization inhibitor in combination and set the reaction temperature to 50 to 1000C. Furthermore, in order to make the reaction proceed smoothly, it is preferable to use known amine compounds, quaternary ammonium salt compounds, etc. as known catalysts.

In order for the surface modifier of the present invention to exhibit excellent surface orientation, it is preferable that the molecular weight is not too high. That is, the fluorine-free polymer portion of the surface modifier of the present invention is dissolved or dispersed in a non-fluorine-based organic solvent, such as dimethylformamide (hereinafter referred to as DMF) or methyl ethyl ketone (hereinafter referred to as MEK), which is a good solvent, and the amount is 20% by weight. %, the viscosity of the solution at 25°C is preferably 10 poise or less, more preferably 5 poise or less. If it exceeds 10 poise, the surface orientation will be insufficient, especially when used as a surface modifier for active energy ray-curable resins.

The compositional analysis of the fluorine-containing block copolymer containing an unsaturated group of the present invention can be performed by known means such as NMR1IR1 elemental analysis.

The surface modifier of the present invention may be in the form of a powder or a polymer solution diluted with a solvent or a reactive diluent.

Properties that can be imparted to polymeric materials by using the surface modifier of the present invention include water and oil repellency, anti-blocking properties, mold release properties, stain resistance, water resistance, acid resistance, solvent resistance, and moisture resistance. This is a function possessed by the fluorine-containing polymer portion of the surface modifier, such as non-adhesion.

The active energy ray-curable polymeric material to which the surface modifier of the present invention is applied is not particularly limited, and any material that is required to have properties that can be imparted by the surface modifier of the present invention can be used. For example, these are paints, inks, adhesives, pressure-sensitive adhesives, sealants, plate-making materials, etc. that can be cured by electron beams or ultraviolet rays, and exhibit a polymer solution form before irradiation with active energy rays, and solid forms after irradiation with active energy rays. , is a material that exhibits a morphology close to that of a solid. The polymer solution refers to a solution that has fluidity at the time of adding the surface modifier of the present invention, and whether it is diluted with a solvent or a reactive diluent or not diluted. Good too. It also includes all materials that are sensitive to active energy rays, and therefore also includes low-molecular compounds that are sensitive to active energy rays. Among these, polymer materials having an acryloyl group or a methacryloyl group before irradiation with active energy rays are more preferable polymer materials because they can achieve sufficient chemical bonding with the surface modifier.

The surface modifier of the present invention is used by being added to a polymer solution of a polymer material to be modified before irradiation with active energy rays. The amount added may be appropriately selected depending on the degree of modification required and the type of polymer material.
If the amount is less than 0.01 parts by weight, sufficient functionality cannot be imparted.

Moreover, if it exceeds 45 parts by weight, the various properties of the polymer material itself may be impaired, so it is preferably in the range of 0.3 to 45 parts by weight.

[Example] The present invention will be specifically described below with reference to Production Examples, Examples, and Comparative Examples. In addition, in each production example, example, and comparative example, % represents weight %.

(Production Example 1) (1) Synthesis of peroxy bond-containing polymer 200 g of MEK was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 70°C without blowing in nitrogen gas.
K232g, methyl methacrylate (hereinafter referred to as MMA)
80g, glycidyl methacrylate (hereinafter referred to as GMA)
120g, fCO(C112), C00(C2)(,0,), C0
A mixed solution consisting of -18 g of (C1h)<C00O] was charged over 2 hours, and the polymerization reaction was further carried out for 5 hours to obtain a solution of a peroxy bond-containing polymer.

The polymerization conversion rates of 4MA and GMA were both 97% or more as a result of measuring the amount of residual monomer using a gas chromatogram (hereinafter referred to as GC). This polymer solution was diluted to 4 times its volume with acetone, and then poured into a large excess of methanol with stirring to re-precipitate the polymer. The precipitated polymer was sufficiently dried to obtain a powdery polymer. G.C.
As a result of analysis, it was confirmed that no monomer remained. The amount of active oxygen in this powdered polymer was 0.12%, and the number average molecular weight in terms of polystyrene measured by gel permeability chromatography (GPC) was 13,000.

(2) Synthesis of block copolymer 28 g of the powdered polymer obtained in (1) above, CF3 (
CF2)7C1(2CH□0COCH=C)I212
A mixed solution of 60 g of MEK and 60 g of MEK was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and a self-reaction reaction was carried out at 70° C. for 15 hours while blowing nitrogen gas. The polymerization conversion rate of the fluorine monomer was 99%. As a result of measuring the amount of active oxygen, it was found that the peroxy bond had almost completely disappeared.

The obtained polymer solution was diluted to 4 times the volume with MEK and poured into a large excess of methanol with stirring to re-precipitate the polymer. The precipitated polymer was sufficiently dried to obtain a fine polymer powder.

30 g of fine powder of this polymer was added to a mixed solvent consisting of 150 g of methanol and 450 g of butyl acetate, and
The mixture was stirred for a period of time to extract one of the by-produced components, a fluorine-free acrylic polymer. Next, the remaining polymer was poured into 600 g of trichlorotrifluoroethane and stirred at 40°C for 48 hours to extract the fluoropolymer.

As a result, it was found that the powder had a composition ratio of block copolymer/fluorine-free acrylic polymer/fluorine-containing polymer of 6.9/2.410.7. Therefore, the weight ratio of the fluorine-containing polymer part [structural unit (A)] and the fluorine-free polymer part [structural unit (B')] in the block copolymer is 34/6.
I found out that it was 6. In addition, as a result of NMR analysis of the block copolymer using deuterium-substituted acetone, it was found that the constituent components of the polymer part that do not contain fluorine were as follows.
The MA/GMA was found to be 40/60.

(3) Introduction of unsaturated groups into block copolymer In a reactor equipped with a reaction thermometer, a stirrer, and a reflux condenser, the
5 g of block copolymer obtained from ) (glycidyl group content is 0.
014 mol), methacrylic acid 0.96 g (0,011
mole), triethylbenzylammonium chloride 0
．． 25g, monomethoxyhydroquinone 0.004g,
A reaction solution was prepared by adding 32.25 g of DMF. Next, the temperature was raised to 100° C. while blowing nitrogen gas, and the reaction was carried out at the same temperature for 6 hours. After the reaction is completed, the polymer solution 2
Weigh out g in 20ml of dioxane and add 0°I of KOH.
As a result of titration with N solution [mixed solution of water/methanol-1/1 (weight ratio)] and quantifying unreacted methacrylic acid, 7
It was found that 5% of methacrylic acid was consumed in the reaction.

Furthermore, the polymer solution was diluted to 3 times the volume with DMF and poured into a large excess of water/methanol - 1/1 (weight ratio) mixed solution with stirring to re-precipitate and purify the polymer. . After thoroughly drying this polymer powder, GPC analysis using DMF as an eluent revealed that low molecular weight compounds such as methacrylic acid were almost completely removed.

DMF was added to this polymer to prepare a 20% solution, and K
As a result of sufficiently drying the film on a transparent Br plate and performing IR analysis, a characteristic absorption derived from the CH2=CH- group was observed near 1640 cm', confirming that an unsaturated group had been introduced. It was done.

Furthermore, as a result of NMR analysis using deuterium-substituted DMF, it was found that a proton peak originating from the CH2=CH- group was newly generated, and a proton peak originating from the glycidyl group was reduced. From the peak area ratio, which also takes into account the peak of the methyl ester proton of the MMA component, 60% of the glycidyl groups before the reaction are CH2=CH-COOCH2C.
It became clear that H(OH)CH2- group was substituted.

As a result, the polymer obtained in this reaction has the structural unit (B)
It was shown that the proportion of the polymer portion having general formula (III) as a unit was 48%, and the weight ratio of structural unit (A)/structural unit (B) was 30/70.

In addition, 20 was prepared by adding MEK to this polymer powder.
% solution had the appearance of a bluish-white dispersion and a viscosity of 1.0 poise at 25°C.

(Production Example 2) Next, in the reaction for introducing an unsaturated group in Production Example 1, the same conditions as in Production Example 1 (3) were used except that 0.48 g (0,0056 mol) of methacrylic acid was used. A block copolymer containing unsaturated groups was obtained. In the polymer obtained by this reaction, the proportion of the polymer portion having the general formula (I) as a unit in the structural unit (B) is 28%, and the proportion of the structural unit (A)/structural unit (B) is 28%. The weight ratio was 31/69. Further, a solution prepared by adding MEK to this polymer powder and adjusted to 20% had the appearance of a bluish-white dispersion, and the viscosity was 0.8 poise at 25°C.

(Production Example 3.4) (1) Synthesis of block copolymer Using the same reactor as used in Production Example 1, charge 150 g of DMF into the reactor, and while blowing nitrogen gas,
Heat to 0°C, 204 g DMF, MMAloog
, HEMA 50g, GMA 50g.

[C0(CH2)4C00(C2H40)3CO(CH
2) Mixed solution consisting of 4COOO1, [+-17g
The mixture was charged over a period of time, and the polymerization reaction was further carried out for 4.5 hours to obtain a peroxy bond-containing polymer. As a result of measuring the amount of residual monomer by GC, the polymerization conversion rate was 98% or more.

Subsequently, 160 g of DMF and C, Fl 3S02N(C2)15)C2)(40CO
A mixed solution of C (C1(3) and 286 g of CH) was added dropwise over 30 minutes, and then heated at 700C for 3 hours and at 77°C for 10 minutes.
A time polymerization reaction was performed.

As a result of GC analysis, the polymerization conversion rate of the monomer was 98% or more. Furthermore, as a result of measuring the amount of active oxygen, it was found that the peroxy bonds had almost completely disappeared.

(2) Reaction for introducing unsaturated groups The polymer solution synthesized in (1) above was diluted with DMF to adjust the active ingredient concentration to 30%. Next, an unsaturated group was introduced into the block copolymer by reaction with an unsaturated group-containing carboxylic acid shown in Table 1.

After preparing the reaction solutions shown in Table 1, the reaction was carried out under the same conditions as in Production Example I. Thereafter, the polymer was diluted to 3 times its volume with acetone and poured into a large excess of a mixed solvent of water/methanol (1/1 weight ratio) with stirring to re-precipitate and purify the polymer.

G in the same manner as in Production Example 1 using sufficiently dried polymer powder.
When PC analysis was performed, it was found that none of the polymers contained low molecular weight compounds. In addition, IR analysis revealed that unsaturated groups were introduced, and NMR
Through analysis, it was possible to determine the amount of unsaturated groups introduced into the polymer. The results are shown in Table-2.

(3) Removal process of by-product polymers 100 g of each polymer powder obtained in the above (2) was added to a mixed solvent consisting of 300 g of methanol, 170 g of toluene, and stirred at 50'C for 8 hours to remove by-product polymers. One component, an acrylic polymer that does not contain fluorine (but does contain unsaturated groups), was extracted. Next, the remaining polymer was poured into 2000 g of trichlorotrifluoroethane,
The fluoropolymer was extracted by stirring at 40°C for 24 hours.

Measure the weight of the extract to determine whether the block copolymer/
The composition ratio of fluorine-free acrylic polymer/fluorine-containing polymer was determined. The weight ratio of the fluorine-containing polymer part [structural unit (A)] and the fluorine-free polymer part [structural unit (B)] in the block copolymer is determined by checking with the introduction rate of unsaturated groups by NMR analysis. Calculated.

Furthermore, the block copolymer after the by-product extraction was dissolved and dispersed in deuterium-substituted acetone and subjected to NMR analysis, and the general formula (III) occupied in the structural unit (B) was determined by the same method as in Production Example 1. The proportion of the polymer portion used as a unit was determined.

Furthermore, the viscosity at 25° C. of a 20% solution prepared by adding MEK to the block copolymer powder was measured. These results are also shown in Table 2.

Table 1 represents the composition ratio of Kyoden-coupled material/fluorine-free polymer/fluorine-containing polymer.

The abbreviations in Table-1 represent the following meanings.

TEBAC: ) Ethylbenzylammonium chloride MMHQ: Monomethoxyhydroquinone Also note (1)
) is the block in 100g of polymer powder Note (2) in Table-2
) indicates the reaction rate (%) between the glycidyl group and the carboxylic acid determined by NMR analysis.

(Production Example 5) When synthesizing a block copolymer, MMA was added during the first stage polymerization.
A block copolymer was synthesized under the same conditions as in Production Example 3 (1) except that 149 g of HEMA and 50 g of GMAl were used.

Regarding the reaction for introducing an unsaturated group, see (2) in Production Example 3.
) The reaction solution shown in Table 3 was prepared under the same conditions as in (2) of Production Example 3, and then the reaction solution was prepared under the same conditions as in Production Example 3 (2).

Furthermore, a polymer powder was obtained in the same manner as in Production Example 3 (2), and IR and NMR analysis was conducted. The obtained polymer powder was made into a 20% M, EK solution, and the viscosity was measured. The results are shown in Table 4.

(Production Example 6) When synthesizing a block copolymer, MMA was added during the first stage polymerization.
Synthesis and analysis were carried out in the same manner as in Production Example 5, using 140 g of HEMA, 50 g of HEMA, and 10 g of GMA, except that the unsaturated group introduction reaction was carried out using the reaction solution shown in Table 3.

(Production Example 7) When synthesizing a block copolymer, MMA was added during the first stage polymerization.
Synthesis and analysis were carried out in the same manner as in Production Example 5, except that 90 g of GMA and 110 g of GMA were used and the unsaturated group introduction reaction was carried out using the reaction solution shown in Table 3.

(Production Example 8) When synthesizing a block copolymer, MMA was added during the first stage polymerization.
Synthesis and analysis were carried out in the same manner as in Production Example 5, except that 70 g of GMA and 130 g of GMA were used and the unsaturated group introduction reaction was carried out using the reaction solution shown in Table 3.

Table-4 The abbreviations in Table-3 represent the following meanings.

TEBAC: Triethylbenzylammonium chloride MMHQ/monomethoxyhydroquinone (Production Examples 9-1
3) (1) Synthesis of peroxy bond-containing polymer Place 300 g of DMF in a reactor equipped with a thermometer, a stirrer, and a reflux condenser.
and heated to 75℃ while blowing nitrogen gas,
Toluene 270g, MMA200g, butyl acrylate (hereinafter referred to as BA) 60g, GMA l 40
g.

−[C0(CHx),C)I(CzHs)(CHz)+
A mixed solution consisting of 30 g of oCOOO]ts was charged over 3 hours, and a polymerization reaction was further carried out for 2 hours to obtain a peroxy bond-containing polymer. As a result of measuring the amount of residual monomer by GC, the polymerization conversion rate was 98% or more. Furthermore, the amount of active oxygen in the obtained polymer solution was 0.08%.

(2) Synthesis of block copolymer The polymer solution obtained in (1) above, the fluorine-containing monomer, and toluene were added in the amounts shown in Table 5, and a blocking reaction was carried out at 75°C. The reaction time and polymerization results are also shown in Table-5.

(3) Reaction for introducing unsaturated groups The polymer solution synthesized in (2) above was diluted with DMF,
The active ingredient concentration was adjusted to 25%. Then,
After preparing the reaction solutions shown in Table 6, a reaction was carried out under the same conditions as in Production Example 1. Thereafter, the polymer was diluted to 3 times its volume with acetone and poured into a large excess of a mixed solvent of water/methanol (1/1 weight ratio) with stirring to re-precipitate and purify the polymer.

When the sufficiently dried polymer powders were subjected to GPC analysis in the same manner as in Production Example 1, it was found that none of the polymers contained low molecular weight compounds. Further, it was possible to determine that unsaturated groups had been introduced into the polymer by IR analysis, and further to determine the amount of unsaturated groups introduced into the polymer by NMR analysis. The results are also shown in Table-6.

Table-5 Table-6 The abbreviations in Table-5 represent the following meanings.

Compound (1)・CI(2=c(C)Is)COOCHJ
(C2Hs)COCsF+s compound (2): CH2
= C) ICOOCH2CtFs (Production Example 14.15) In order to contrast with Production Example 3.4, (1) of Production Example 3
The same block copolymer and isocyanate compound, H
An unsaturated group introduction reaction was carried out by reacting EMA (Production Example 14) or HEA (Production Example 15).

That is, in the same reactor as in Production Example 3, 120 g of the same 30% polymer solution used in Production Example 3 (2) was charged, and in addition, a biuret form of hexamethylene diisocyanate (trade name, manufactured by Asahi Kasei Corporation) was charged. Duranate 24A
) and 200 ppm of dibutyltin dilaurate were charged, heated to 70°C, and reacted for 4 hours. Next, after cooling the reaction solution to room temperature, 54 g of HEMA (Production Example 14) or 48 g of HEA (Production Example 15) and 50 ppm of hydroquinone dimethyl ether were added, heated to 65° C., and reacted for 4 hours. After the reaction was completed, the mixture was diluted to twice the volume with acetone and poured into a large excess of methanol with stirring to re-precipitate and purify the polymer.

MEK was added to the sufficiently dried polymer powder of Comparative Example 1 to prepare a 20% by weight solution, but it was difficult to dissolve and disperse it.
It took a longer time than in Example 6. When the viscosity was measured at 25°C, it was 11 poise. The compound of Production Example 15 gelled during drying and could not be redissolved.

(Production Examples 16 to 18) In order to compare with Production Examples 10 to 12, random copolymers were synthesized using the monomers shown in Table 7. Next, an unsaturated group introduction reaction was carried out in the same manner as in Production Examples 10 to 12 to obtain a fluorine-containing random copolymer containing an unsaturated group.

That is, to prepare the random copolymer, 181 g of DMF was placed in the same reactor as in Production Example 10, and 81 g of DMF was charged while blowing nitrogen gas.
The monomer, CH3(C
H2)3CH(C2H5)COOOC(C1(3)31
A mixed solution of 0g of toluene and 180g of toluene was added dropwise over 2 hours, and the mixture was further reacted at the same temperature for 10 hours.

The conversion rate of each monomer by GC analysis was 97% or more. The resulting polymer solution was diluted with DMF to give a 25% solution.

The reaction for introducing an unsaturated group was carried out under the same conditions and in the same manner as in (3) of Production Examples 10 to 12.

Contains no low molecular weight compounds based on GPC analysis,
IR analysis revealed that unsaturated groups were introduced. Carboxylic acid reaction rate in the same manner as Production Examples 10 to 12,
The reaction rate of glycidyl groups was measured.

Compound (1) and compound (2) in Table 7 are the same as those in Table 5.
represents compound (1) and compound (2), respectively.

(Examples 1 to 11 and Comparative Examples 1 to 12) Production Examples 1 to 4,
Production Example 1 (2), Production Example 3 (1) and (2), Production Example 4 (1) and (2), Production Examples 5 to 14, Production Example 16
The performance of the fluoropolymer obtained in steps 1 to 18 as a surface modifier was evaluated.

Epoxy acrylate (product name S manufactured by Showa Kobunshi Co., Ltd.)
A solution consisting of 80 g of P-1506), 60 g of urethane acrylate (trade name M1100 manufactured by Toagosei Kagaku Kogyo Co., Ltd.), 10 g of benzoin isobutyl ether, and 450 g of MEK was prepared.
A test solution was prepared by adding a predetermined amount of a 5% fluoropolymer solution.

Note that this 25% fluoropolymer solution was prepared in Production Example 1 (
Regarding the polymer in 2), MEK was used at 25%,
Production Example 3 (1) and Production Example 4 (1) were obtained by diluting the synthesized polymer solution directly with MEK to make a 25% solution, and the others were those used for viscosity measurement in Production Examples. Using.

Next, it was coated on an aluminum plate (trade name Al100, manufactured by Nippon Test Panel Co., Ltd.) using a bar coater so that the dry film thickness was 20 μm, and then heated and dried at 80° C. for 10 minutes to prepare a test plate. Add this cured film to acetone and 10% sulfuric acid water for 4 hours.
It was immersed for 8 hours, and the water and oil repellency of the surface before and after immersion was evaluated. The results are shown in Tables 8 to 12.

In addition, a 5 cm wide adhesive tape made by Sekisui Chemical Co., Ltd. was pressed onto the cured coating film by moving a 2 kg roller back and forth twice, and after being left at 500C for 3 days, the tape was peeled off to clean the tape surface. ESCA analysis (analysis using an X-ray photoelectron analyzer) was conducted to evaluate whether there was any transfer of fluorine components. The results are also shown in Tables 8 to 12.

Table-8 Table-9 Table=1 Table-10 From the results of Tables-8 to Table-12 above, it is clear that when the surface modifier of the present invention is added to active energy ray-curable resin, the function of fluorine on the surface It was found that water and oil repellency can be imparted. In particular, it was revealed that the water and oil repellency hardly decreased even after immersion in acetone, and that the modification effect was extremely durable due to chemical bonding with the matrix polymer. It was also found that there was no transfer of fluorine components to the adhesive tape. From the comparison of Examples 3 and 4 and the comparison of Examples 5 and 6, even if the surface modifier contains a homopolymer produced as a by-product during block copolymer production, the surface modifier functions equally well. I found out that there is.

On the other hand, as shown in Comparative Example 2.3.4, with a block copolymer that does not have unsaturated groups, there is no decrease in performance after immersion in sulfuric acid water, but water and oil repellency decreases after immersion in acetone. showed a trend. Furthermore, when the amount added was high, slight transfer of the fluorine component to the adhesive tape was observed. Furthermore, Comparative Examples 5 to 8 showed a tendency for either the initial modification effect or the sustainability of the modification effect to be insufficient.

Furthermore, in the case of a block copolymer in which unsaturated groups were introduced using an isocyanate compound (Comparative Example 9), the initial modification effect tended to be insufficient. For random polymers (
In Comparative Examples 10 to 12), it was observed that the surface activity was lower than that of block copolymers having the same composition, the initial modification effect was low, and the fluorine component was transferred.

(Examples 12 to 16, Comparative Examples 13 to 18) Production Example 3, Production Example 3 (2), Production Examples 10 to 12, Production Example 3 (1)
The performance of the fluoropolymers obtained in Production Example 14 and Production Examples 16 to 18 as a surface modifier was evaluated.

Neopentyl glycol acrylate 30g, pentaerythritol tetraacrylate 30g, acrylic acid-2
- Ethylhexyl 20g, oligoester acrylate (trade name M-6200 manufactured by Toagosei Chemical Industry Co., Ltd.) 2
An active energy ray-curable resin containing 0 g was prepared.

A predetermined amount of the fluoropolymer powder of each production example was added to 100 g of this resin, and dissolved and dispersed. Next, the film thickness was 30 μm.
A cured film was prepared by applying an electron beam of 10 Mrad at an acceleration voltage of 170 KV in a nitrogen atmosphere using an electrocurtain manufactured by ESI. The same test as in Example 1 was conducted on the obtained cured film. The results are shown in Tables 13 to 15.

Table-14 Table-15 From the results in Tables-13 to Table-15 above, when the block copolymer of the present invention is added to active energy ray-curable resin, the surface has water and oil repellency, which is the function of fluorine. I found out that it can be granted. In particular, even after immersion in acetone, the water and oil repellency hardly deteriorated, and it was found that the modification effect was extremely long-lasting due to chemical bonding with the matrix polymer.

On the other hand, the block copolymer having no unsaturated groups (Comparative Example 14) showed a tendency for the water and oil repellency to decrease slightly after immersion in acetone. In addition, block copolymers (Comparative Example 15) and random copolymers (Comparative Examples 16 to 18) into which unsaturated groups were introduced by reaction with an isocyanate compound tended to lack initial modification effects.

(Examples 17-21 and Comparative Examples 19-22) Production Example 1.
2. Performance as a surface modifier of the fluoropolymer obtained in Production Example 4 (1) and (2), Production Example 10.11, and Production Example 16.17 was evaluated.

Tetrahydrofurfuryl acrylate was added to the fluoropolymer powder to prepare a 20% solution. In addition, 50 g of urethane acrylate (trade name UN-5200 manufactured by Negami Kogyo Co., Ltd.) was used as an active energy ray-curable resin.
, 26 g of tetrahydrofurfuryl acrylate, 20 g of trimethylolpropane triacrylate, photoinitiator (
A solution containing 4 g of Darocure-1173 (trade name, manufactured by Merck & Co., Ltd.) was prepared.

Next, a predetermined amount of a 20% fluoropolymer solution was added to 100 g of active energy ray-curable resin, and coated with a bar coater to a polycarbonate plate (trade name: Kneepilon, manufactured by Mitsubishi Gas Chemical Co., Ltd., to a film thickness of 15 μm). Plate thickness 1mm
) and prepared a test plate. For this test board, 2
A UV-cured coating film was obtained by irradiating with a Kw high-pressure mercury lamp from a distance of 20 cm for 25 seconds.

A rubbing test was conducted in which the surface of this UV-cured coating was rubbed 20 times with a Kimwipe soaked in an acetone/ethanol mixed solvent (weight ratio: 1/1). The following evaluations were made before and after this test. The results are shown in Tables 16 and 17.

The contact angle of oil-repellent nidodecane was measured.

Stain resistance: Black marker ink was applied, left for one week, and then wiped off with ethanol to evaluate the appearance.

◎: No trace remains at all.

○: Some marks remain, but the appearance is not impaired.

△: Traces remain to the extent that the appearance is impaired.

×; Traces remain completely.

Non-adhesiveness: An adhesive tape manufactured by Sekisui Chemical Co., Ltd. with a width of 5C [I+ is pressed onto the cured film using a 2 kg roller that moves back and forth twice, and after being left at 3-0°C for 3 hours, the adhesive tape is Tensile test was performed and 180 degree peel strength (g/am)
was measured.

From the results in Tables 16 and 17, it is clear that when the block copolymer of the present invention is added to active energy ray-curable resin, the surface has oil repellency, stain resistance, and non-adhesive properties, which are the functions of fluorine. It has become clear that it can be granted. Even after the rubbing test, these performances hardly deteriorated, and it was found that the modification effect was extremely durable due to chemical bonding with the matrix polymer.

On the other hand, the block copolymer having no unsaturated groups showed a tendency to decrease in oil repellency, stain resistance, and non-adhesion after the rubbing test (Comparative Example 20). Furthermore, the random copolymers (Comparative Examples 21 and 22) showed a tendency for the initial modification effect to be insufficient.

〔Effect of the invention〕

According to the first aspect of the present invention, the active energy ray-curable surface modifier for polymeric materials comprises a fluorine-containing polymer part and a polymer part into which an unsaturated group sensitive to active energy rays has been introduced. When this surface modifier is added to a polymer material, the fluorine-containing polymer portion in the surface modifier is oriented on the surface of the polymer material, and the fluorine-containing polymer is The combined part exhibits properties such as water and oil repellency, anti-blocking property, mold releasability, antifouling property, water resistance, acid resistance, solvent resistance, moisture resistance, etc., and the unsaturated group in the surface modifier. The polymer portion into which active energy rays are introduced exhibits miscibility with the polymeric material, and when irradiated with active energy rays, it chemically bonds with the polymeric material and has the excellent effect of sustaining the modification effect over a long period of time. .

Further, according to the second invention, even if the structural unit (A) in the block copolymer has a predetermined amount of a polymer moiety derived from general formula (II), The effect is that the effect is effectively exhibited.

Furthermore, according to the third invention, after the monomer represented by general formula (II) and the monomer represented by general formula ((IV) are polymerized under predetermined conditions in the first stage polymerization, , reacting a fluorine-containing polymer obtained by polymerizing a monomer represented by general formula (I) under predetermined conditions in the second stage polymerization with a compound represented by general formula (V). This provides an excellent effect in that the desired surface modifier made of a block copolymer can be easily obtained in a state where thermal polymerization of unsaturated groups is suppressed based on addition reaction.

Further, according to the fourth invention, in addition to the monomer represented by general formula (I) in the second stage polymerization in the third invention, in addition to the monomer represented by general formula (I),
By using the monomer represented by II), the third
This invention has the same effect as the invention of .

Claims (1)

[Claims] 1. Structural unit (A) derived from the following general formula (I)
and a structural unit (B) consisting of a polymer moiety derived from the following general formula (II) and a polymer moiety having the following general formula (III) as a unit, and the general formula (
III) The proportion of the polymer portion as a unit is 1 to 70% by weight
An active energy ray-curable surface modifier for polymeric materials comprising a block copolymer having a structural unit (A)/structural unit (B) ratio of 80/20 to 10/90 by weight. CH_2=CR_1COOR_2Rf・・・・・・(
I) In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is -
C_pH_2_p-, -C(C_pH_2_p_+_1
)H-, -CH_2C(C_pH_2_p_+_1)H
-or -CH_2CH_2O-, Rf is C_nF_2_
n_+_1, (CF_2)_nH, (CF_2)_pO
C_mH_2_mC_lF_2_l_+_1, (CF_
2)_pOC_mH_2_mC_lF_2_lH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables etc.▼. However, p is 1 to 10, n is 1 to 16, and m is 0 to
10 and 1 are integers from 0 to 16. CH_2=CR_3R_4...(II) In the formula, R
_3 is a hydrogen atom or a methyl group or CH_2COOH, R
_4 is COOR_5 (in the formula, R_5 is a hydrogen atom, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ , -CH_2CH_2N (C_sH_2_s_+_1,
)_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_
2CH=CH_2, linear or branched C_nH_2_n_+_1, linear or branched C_pH_2_p_+_1OH, -CH_
2CH(OH)CH_3, (C_2H_4O)_rC_
sH_2_s_+_1, [CH_2CH(CH_3)O
]_rC_sH_2_s_+_1. However, P is 1 to 10, n is 1 to 16, r is 2 to 20, and s
is an integer from 0 to 8. ), -CONR_6R_7 (wherein R_6 is a hydrogen atom or C_pH_2_p_+_1,
R_7 is a hydrogen atom, linear or branched C_pH_2_
p_+_1, or CH_2OH. However, p is 1~
It is an integer of 10. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼, -CONHC(CH_3)_2CH_2COCH_3, -CONHC(C
H_3)_2CH_2SO_3H, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CN or -OCOC_nH_2_n
___+_1 (where n is an integer of 1 to 16, linear,
It may be branched. )▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・(III) In the formula, R_3 is a hydrogen atom or a methyl group, and R_9 is CH_
2=CH-, CH_2=C(CH_3)-. 2. A claim characterized in that the structural unit (A) consists of 40% by weight or more of a polymer portion derived from general formula (I) and 60% by weight or less of a polymer portion derived from general formula (II). Item 1. The active energy ray-curable surface modifier for polymeric materials. 3. In the first stage polymerization, polymeric peroxide is used as a polymerization initiator, and one or more monomers represented by the above general formula (II) and a monomer represented by the following general formula (IV) are used. The weight ratio of monomer represented by general formula (II)/monomer represented by general formula (IV) = 99/1 to 4
After polymerization under 0/60 conditions, in the second stage polymerization,
One or more of the monomers represented by the general formula (I) are used in the first stage polymerization and the second stage polymerization in a weight ratio of 90/10 to 20/80. A fluorine-containing polymer obtained by polymerization under the following conditions and the following general formula (
An active energy ray-curable type, characterized in that a block copolymer is produced by reacting the compound represented by formula (V) with the glycidyl group in the fluoropolymer and the compound represented by general formula (V). A method for producing a surface modifier for polymeric materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) In the formula, R_8 is a hydrogen atom or a methyl group. R_9-COOH... (V) In the formula, R_9 is CH_2=CH-, CH_2=C(CH
_3)-. 4. In the second stage polymerization, 40% by weight or more of one or more monomers represented by general formula (I) and one or more monomers represented by general formula (II) 4. The method for producing an active energy ray-curable surface modifier for polymeric materials according to claim 3, characterized in that two or more types are copolymerized in an amount of 60% by weight or less.